This invention relates in general to the process for the production of allyl halide amine compounds and poly(allyl halide amine) copolymer and their reaction products by using an oxidized silicon compound as the catalyst to polymerize the allyl halide with amine compounds.
Various silicon acids, silica, silicates containing silicon acids and silicates that will react with the halides in the allyl halides to produce silicon acids may be used as the catalyst. Various silicon acids such as silicoformic acid, polysilicoformic acid, hydrated silica and natural silicates containing free silicic acid radicals may be used as the catalyst. Various alkali silicates that will react with the halide in allyl halide such as alkali metal silicates, and alkaline earth metal silicates including sodium silicate, potassium silicate, lithium silicate, calcium silicate, cadmium silicate, barium silicate, zinc silicate, barium silicate, magnesium silicate, aluminum silicate, etc. may be used as the catalyst.
Silica may be heated in a dilute aqueous alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, in the ratio of about 1 to 1 mols, until the water evaporates thereby producing a mono alkali metal silicate which may be used as the catalyst in this invention. Hydrated silica is the preferred catalyst and is preferred to be in a fine granular form. The silicoformic acid may be produced by the methods outlined in U.S. Pat. No. 3,674,430. Hydrated silica may be produced by any of the commonly known methods.
Some of the natural occuring silicates that may be used in this invention are clay, kaolin, silica, talc, asbestos, natrolite, garnet, mica, feldspar, beryl etc. and mixtures thereof.
The natural occuring silicates may be treated with a dilute mineral acid to produce more active silicic acid radicals present in the silicates.
Allyl halides may be produced by the addition of a halide to propylene. Methallyl halides may be produced by the addition of a halide to isobutylene. Other compounds with the combination ##STR1## which is known as the allylic system, may be used in this invention. Allyl chloride is the preferred allyl halide.
Various mono-olefinic allyl type mono-halide with the essential grouping of atoms which may be represented as ##STR2## wherein R is a hydrogen or a C.sub.1 to C.sub.4 alkyl group wherein X represents a halogen atom. Furthermore, these compounds contain only one olefinic group of which one of the unsaturated carbon atoms contains at least one hydrogen atom per molecule.
Representive examples of mono-olefinic allyl type mono-halides are such compounds as allyl chloride, allyl bromide, crotyl chloride, crotyl iodide, beta-methylallyl chloride, beta-methylallyl bromide, methyl vinyl carbinyl fluoride, alpha-dimethyl-allyl chloride, beta-cyclohexylallyl chloride, cinnamyl chloride, beta-ethyl-crotyl chloride, beta-phenylallyl bromide, alpha-dicyclohexylallyl chloride, beta-propylallyl iodide, beta-phenyl-allyl chloride, beta-cyclohexylallyl fluoride, 2-chloromethyl butene-1,2-chloromethyl pentene-1,2-chloromethyl hexene-1 and mixtures thereof.
Various organic amine compounds may be used in this instant invention such as alkylenepolyamines, alkylenimines, arylenediamines, alkyleneamines, aryleneamines, condensation products of an epihalohydrin and a poly(alkylene polyamine), ammonia, condensation products of epichlorohydrin and ammonia, hydrazine, alkanolamines, aminoethyl alkanolamine and mixtures thereof.
The alkylenepolyamines which may be used in this invention are well known compounds corresponding to the formula H.sub.2 N((CH.sub.2).sub.y NH).sub.x --H in which x is one or more and y is an integer having a value of 4 to 10. Typical amines of this class are the alkylenediamines such as, 1,6-diamino-3-methyl-n-hexane, 1,3-propylenediamine 1,4-diamine-n-butane; 1,6-diamine-n-hexane, 1,10-diamino-n-decane and polyalkylenepolyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the corresponding polypropylenepolyamines and polybutylenepolyamines. Arylenediamines such as p-phenylenediamine may be used. Arylenedipolyamines may be used. Polyamide polymers with free amine radicals may be used in this instant process.
Various aliphatic and aromatic mono-amines such as methylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, aniline, toluidine amine, xylidine amine, naphthylamine, benzylamine, vinyl amines and mixtures thereof may be used in this process, or they may be mixed with the polyamines and used in this process.
Various organic compounds containing an amine radical may be used in this process such as aminocaproic acid, aminobenzoic acid, vinyl amines, fatty acid amides, hydroxy amines, and mixtures thereof.
The polyamines may first be reacted with dicarboxyl acids, dicarboxyl anhydrides, epoxy compound and carbon disulfide to produce polyamine compounds with unreacted amine groups that may be used in this invention.
The organic polyamine compounds may be reacted chemically with silica, hydrated silica, and silicoformic acid to produce an organic polyamine silicate compound then may be reacted chemically with the allyl halide compound to produce a poly(mono-olefinic allyl type mono-halide amine silicate) copolymer.
Various polyamide resins containing 2 or more active amine radicals per molecule may be used in this invention. The polyamide resins may be produced by any of the commonly known methods.
Polyfunctional polyamines will also act as a cross-linking agent with poly(allyl halide) polymers and in the production of poly(ally halide amine) polymers. Bifunctional amines and polyfunctional amines may be mixed then reacted with the allyl halides to produce thermosetting resins. Various bifunctional amines may be used such as methylamine, ethylamine, ethanolamine, propylamine, N,N'-dimethylenediamine, piperazine, aniline, etc. Various polyfunctional polyamines may be used such as ethylenediamine, N-methylenediamine, polyalkylenepolyamines, polypropylenepolyamines, p-phenylenediamine; p,p'-bisaniline; 1,3-diamino-2-propanol, 1 mol of ammonia reacted with 3 mols of epichlorohydrin, etc. The reaction is enhanced by the presence of an alkali catalyst.
The allyl halide amine compound and polymer may be further reacted chemically with cross linking agents such as aldehydes, ketones, organic dicarboxyl acids, organic dicarboxyl anhydrides, aliphatic dihalide compounds, aliphatic trichlorides, sulfur, dihydroxy phenols, cyanides, lignin, epoxy compounds and resins, epihalohydrins, halohydrins, isocyanates, furan compound, thiocyanates, polyester, resins with 2 or more carboxyl acid radicals per molecule, acrylate polymers, polysulfides, sodium polysulfides, silicon acids, silicon tetrachloride, carbon disulfide and mixtures thereof to produce resins that can be used as adhesives, coating agents, impregnants, molding resins and powders, thermosetting resins, thermoplastic resins, etc.